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The structural and magnetic properties of two mixed-valence cobaltites with a formal population of 0.30 Co4+ ions per f.u., (Pr1−yYy)0.7Ca0.3CoO3 (y=0 and 0.15), have been studied down to very low temperatures by means of high-resolution neutron diffraction, SQUID magnetometry and heat-capacity measurements. Combining this complex experimental research with calculations from the first priciples we determined character of spin states in cobalt ions. Furthermore, the role of rare earth elemtents in phase transitions of cobaltites with perovskite structure was clarified (see image).